UNIVERSITI PUTRA MALAYSIA
SYNTHESIS AND CHARACTERIZATION OF ZnO
PARTICLES AND MWNTs-ZnO NANOCOMPOSITES
SUZANITA BINTI LATIP
FS 2012 67
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SYNTHESIS AND CHARACTERIZATION OF ZnO
PARTICLES AND MWNTs-ZnO NANOCOMPOSITES
SUZANITA BINTI LATIP
MASTER OF SCIENCE
UNIVERSITI PUTRA MALAYSIA
2012
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SYNTHESIS AND CHARACTERIZATION OF ZnO PARTICLES AND MWNTs-
ZnO NANOCOMPOSITES
By
SUZANITA BINTI LATIP
Thesis Submitted to the School of Graduate Studies, Universiti Putra Malaysia, in
Fulfilment of the Requirement of the Degree of Master of Science
July 2012
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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment
of the requirement for the degree of Master of Science
SYNTHESIS AND CHARACTERIZATION OF ZnO PARTICLES AND
MWNTs-ZnO NANOCOMPOSITES
By
SUZANITA BINTI LATIP
July 2012
Chair : Professor Mohd Zobir Bin Hussein, PhD
Faculty : Science
Multi-walled carbon nanotubes (MWNTs) were functionalized using various acid
treatments to introduce functional groups, especially carboxylic acid groups on the
surface of MWNTs. Different acid solutions namely nitric acid, citric acid, chromic
acid and mixture of nitric and sulphuric acid were used for this purpose.
There are different parameters that had been used for the synthesis MWNTs-ZnO
nanocomposites, including different acid treatments, the ratios between MWNTs and
zinc precursor and surface adsorption of anionic and cationic surfactants. Each
parameter was explored to investigate the effect on the physio-chemical properties of
the MWNTs-ZnO nanocomposites prepared by simple, co-precipitation methods.
Through various acid treated of MWNTs, ZnO nanoparticles were selectively
attached to the nanotubes and the presence of functional groups were further
confirmed. MWNTs-ZnO nanocomposites that were prepared by pre-treatment of
MWNTs with different acids gave dispersion of ZnO nanoparticles attached on the
MWNTs but it was not formed uniformly on the surface of the MWNTs. Each of
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MWNTs-ZnO nanocomposites prepared by pre-treatment of MWNTs with different
acids gave different morphologies such as thin flake ZnO nanoparticles shown by
FESEM study. On the other hand, different ratios between MWNTs and zinc
precursors gave ZnO nanoparticles time to formed different shapes on the surfaces of
MWNTs such flower-like shape.
By verifying the ratios of MWNTs and the precursors, the newly formed of ZnO
nanoparticles morphologies such as flower-like ZnO nanoparticles attached on the
MWNTs lead to new properties of MWNTs-ZnO nanocomposites. The ratio of 1:0.5
between MWNTs to Zn leads to better dispersion in the formation of ZnO on the
surface of MWNTs. The increase in the ratios of MWNTs to ZnO leads the
agglomeration of ZnO nanoparticles and increased the size of ZnO.
The morphologies of ZnO nanoparticles showed non-uniform, long finger-like
irregular granular structure and rod-like structure when it was synthesized by co-
precipitation method, with the addition of CTAB and SDS, respectively. The surface
adsorption of Sodium dodecyl sulphate (SDS) and cetyltrimethylammonium bromide
(CTAB) enable the decoration of MWNTs with a uniform size of zinc nanoparticles.
MWNTs-ZnO nanocomposites prepared with addition of surfactants gives better
distribution of ZnO nanoparticles formation on the surface of MWNTs and decreased
their particle size to 15 nm.
The main problem in this research is the agglomeration of ZnO nanoparticles. They
were agglomerated on the surface of MWNTs and makes the potential properties of
the nanocomposites cannot fully discover. The inertness of MWNTs were also a
challenge, but it has overcome with vary the type acid used.
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The use of green beans as biotemplating agent showed that, ZnO nanoparticles can
be formed with desired morphology and dimension. The result indicates that several
surface morphology can be formed by adjusting the concentration of precursor
solution. The average diameter of the particles was less than 1 m. The green beans
are thought to be responsible to control the size and morphology of the resulting ZnO
nanoparticles by biotemplating process.
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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai
memenuhi keperluan ijazah untuk Master Sains
SINTESIS DAN PENCIRIAN ZnO PARTIKEL DAN MWNTs-ZnO
NANOKOMPOSIT
Oleh
SUZANITA BINTI LATIP
Julai 2012
Pengerusi : Profesor Mohd Zobir Bin Hussein, PhD
Fakulti : Sains
Karbon nanotiub (KNTs) dipelbagai fungsi, menggunakan pelbagai rawatan asid
untuk memperkenalkan kumpulan berfungsi, terutamanya asid karbosilik pada
permukaan KNTs. Pelbagai jenis asid digunakan iaitu asid nitrik, asid sitrik, asid
kromik dan campuran asid nitrik dan sulfurik untuk tujuan ini.
Parameter yang berbeza telah digunakan dalam sintesis KNT bersama zink oksida,
termasuklah asid yang berbeza, nisbah berat antara karbon nanotiub dan zink oksida
nanopartikel (ZnO), dan serapan permukaan oleh kationik dan anionic surfaktan.
Kesan setiap parameter ke atas sifat fizik-kimia KNT-ZnO yang dihasilkan
menggunakn cara pemendakan telah dikaji.
Melalui rawatan pelbagai asid ke atas KNT, zink oksida secara terpilih malekat pada
permukaan nanotiub dan lokasi kumpulan berfungsi telah disahkan. Rawatan
pelbagai asid ke atas KNT-ZnO nanokomposit telah menghasilkan zink oksida
nanopartikel yang melekat pada KNT secara tidak menyeluruh. Tetapi, setiap satu
KNT-ZnO nanokomposit yang disediakan dengan cara ini menghasilkan kelainan
pada morfologi seperti kepingan nipis zink oksida nanopartikel.
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Dengan mempelbagaikan nisbah berat KNT dan zink ion, morfologi zink oksida
yang baru terbentuk seperti zink oksida berbentuk bunga yang boleh menjadikan ia
satu ciri baru untuk KNT-ZnO nanokomposit. Nisbah 1:0.5 antara KNT kepada zink
ion memberi penyebaran yang lebih sekata dalam pembentukan ZnO pada
permukaan KNT. Nisbah peningkatan zink ion dalam nisbah berat ini menyebabkan
penggumpalan ZnO nanopartikel dan ini meningkatkan saiz ZnO.
Morfologi ZnO nanopartikel yang dipengaruhi surfaktan; SDS dan CTAB
menunjukkan tidak keseragaman struktur berbentuk jari dan rod apabila disintesis
dengan menggunakan kaedah pemendakan. Penggunaan surfaktan menyebabkan
penyebaran pembentukan ZnO yang lebih sekata pada pemukaan KNT dan
menyebabkan penurunan saiz ZnO sehingga 15 nm.
Masalah utama dalam kajian ini adalah pengumpulan ZnO nanopartikel. Ianya
mengumpul di atas permukaan KNT dan menyebabkan potensi sifat nanokomposit
tidak dapat ditunjukkan. Sifat lengai KNT juga satu cabaran, tapi ia dapat diatasi
dengan menggunakan pelbagai jenis asid.
Penggunaan kacang hijau sebagai agen biotemplat manyebabkan ZnO nanopartikel
dapat dibentuk dengan morfologi yang diingini dan dimensi yang spesifik. Hasil
kajian menunjukkan pelbagai morfologi dapat dibentuk melalui kepelbagaian
kepekatan cecair prekursor. Diameter purata pada setiap ZnO partikel yang dibentuk
adalah kurang daripada 1 micrometer. Jadi, penggunaan kacang hijau sebagai agen
biotemplat dapat mengawal saiz dan morfologi dalam sistesis ZnO partikel.
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ACKNOWLEDGEMENTS
In the name of Allah, the Most Gracius, the Most Merciful. Only by His help,
blessing and guidance, this master project and thesis can be completed.
I would like to take this oppurtunity to acknowledge and thank for the effort of who
supported my graduate studies in general and the research in particular. First, I wish
to express my sincere thanks and gratitude to my supervisor Prof. Dr. Mohd Zobir
Hussein for his amicable guidance, encouragement, constructive criticism and kind
advice throughout the course of study. I would like to acknowledge the members of
my advisory committee; Dr Siti Halimah Sarijo and Prof Dr Zulkarnain Zainal for
their encouragement, valuable suggestions and advice in many aspects of my
research project to make this possible.
I am greatly thankful for the Special Grantt Research Assistance (SGRA) that
granted financial support during my tenure of study. I would also like to
acknowledge my fellow graduate students: Shazlin, Salwani, Hanim Salami, Sharina,
Sook Keng, Sook Mey, kak Wani, Ana, Lisa, Sumaiyah and everyone in chemistry
department for their support, understanding and co-operation besides being good
freinds. I am grateful for their help and encouragement throughout the research and
writing process. Last, but not least, I would like to dedicate this thesis to my beloved
parents and my family who paid immense sacrifice for the success in my master
research.
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I certify that a Thesis Examination Committee has met on the 13th
July 2012 to
conduct the final examination of Suzanita binti Latip on her thesis entitled Synthesis
of ZnO particles and MWNTs-ZnO nanocomposites in accordance with the
Universities and University Colleges Act 1971 and the Constitution of the Universiti
Putra Malaysia [P.U. (A) 106] 15 March 1998. The committee recommends that the
student be awarded the degree of Master of Science.
Members of the Thesis Examination Committee were as follows:
Y. Bhg. Prof. Dr. Gwendoline Ee Cheng Lian
Professor
Faculty of Science
Universiti Putra Malaysia
(Chairman)
Prof. Madya Dr. Nor Azah binti Yusof
Professor
Faculty of Science
Universiti Putra Malaysia
(Internal Examiner)
Y. Bhg. Prof. Dr. Md Jelas b Haron
Professor
Faculty of Science
Universiti Putra Malaysia
(Internal Examiner)
Dr Sharif Hussein Sharif Zein
Professor
Faculty of Chemical Engineering
Univeriti Sains Malaysia
(External Examiner)
_________________________
SEOW HENG FONG, PhD
Professor and Deputy Dean
School of Graduate Studies
Universiti Puta Malaysia
Date: 21th March 2013
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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been
accepted as fulfilment of the requirement for the degree of Master of Science. The
members of the Supervisory Committee were as follows:
Mohd Zobir bin Hussein, PhD
Professor
Faculty of Science
Universiti Putra Malaysia
(Chairman)
Zulkarnain bin Zainal, PhD
Professor
Faculty of Science
Universiti Putra Malaysia
(Member)
Siti Hamilah binti Sarijo, PhD
Lecturer
Faculty of Applied Science
Universiti Teknologi Mara (UiTM)
(Member)
_______________________________
BUJANG BIN KIM HUAT, PhD
Professor and Dean
School of Graduate Studies
Universiti Putra Malaysia
Date:
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DECLARATION
I declare that the thesis is my original work except for quotations and citation which
have been dully acknowledged. I also declare that it has not been previously, and is
not concurrently, submitted for any other degree at Universiti Putra Malaysia or at
any other institution.
________________________
SUZANITA BINTI LATIP
Date: 13 July 2012
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TABLE OF CONTENTS
Page
ABSTRACT ii
ABSTRAK iv
ACKNOWLEDGEMENTS vii
APPROVAL x
DECLARATION xvi
LIST OF TABLES xiv
LIST OF FIGURES xvi
LIST OF ABBREVIATION xx
CHAPTER
1 INTRODUCTION
1.1 Carbon Nanotubes (CNTs) 1
1.1.1 Overview 1
1.1.2 Structure and Properties of CNTs 1
1.1.3 Application of CNTs 3
1.1.3.1 MWNTs in Electronics 4
1.1.3.2 MWNTs in Energy Application 4
1.1.3.3 MWNTs Sensors 4
1.1.3.4 MWNTs in Biological Application 4
1.2 Zinc Oxide nanoparticles 5
1.3 Development of MWNTs Nanocomposites 6
1.4 Synthesis inorganic materials using bio template processes 7
1.5 Statement of Problem 8
1.6 Significant of Study 9
1.7 Objective of Study 11
2 LITERATURE REVIEW
2.1 Surface modification of MWNTs 12
2.1.1 Overview 12
2.1.2 Acid treatment of MWNTs 13
2.2 MWNTs-metal oxide nanocomposites 15
2.2.1 Overview 15
2.2.2 Preparation of MWNTs-metal oxide nanocomposites 15
2.2.3 Simple co-precipitation method synthesized MWNTs
nanocompoites
17
2.2.4 Application of MWNTs nanocomposites 18
2.3 Surfactants in MWNTs nanocomposites 19
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2.4 Morphological and size variation of metal oxide in CNTs
nanocomposites
20
2.5 ZnO biotemplating processes 21
2.5.1 Bio-template agent 21
2.5.2 Morphologies controlled using bio-template agent 21
3 METHODOLOGY
3.1 Materials 23
3.2 Methodology 23
3.2.1 Modification MWNTs with different of acid treatment 23
3.2.2 Synthesis MWNTs-ZnO nanocomposites 24
3.2.3 Synthesis ZnO Particles 26
3.3 Characterization 26
3.3.1 Powder X-Ray Diffraction 26
3.3.2 Field Emission Scanning Electron Microscopy (FESEM) 27
3.3.3 Fourier Transform Infrared Spectroscopy (FTIR) 27
3.3.4 Surface Area and Porosity Measurement 28
3.3.5 Raman 29
3.3.6 Carbon, Hydrogen, Nitrogen and Sulfur Analysis (CHNS) 29
3.3.7 Thermogravimetric analysis (TGA) 30
3.3.8 Ultraviolet – Visible Light Spectroscopy 30
4 RESULT AND DISCUSSION
4.1 Modification of MWNTs with different of acid treatment 32
4.2 Synthesis MWNTs-ZnO nanocomposites 45
4.2.1 Synthesis of MWNTs-ZnO nanocomposites using acid-
treated MWNTs
45
4.2.2 The effect of weight ratio of MWNTs to Zn precursor 57
4.2.3 Effect of surfactants on synthesis MWNTs-ZnO
nanocomposites
71
4.3 Synthesis ZnO particles 83
4.3.1 Effect of surfactants on synthesis ZnO particles 83
4.3.2 Synthesis ZnO particles using green beans as
biotemplating agents
91
5 SUMMARY, CONCLUSION AND RECOMMENDATIONS FOR
FUTURE RESEARCH
100
REFERENCES/BIBLIOGRAPHY 104
BIODATA OF THE STUDENT 110
LIST OF PUBLICATIONS 111
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